Hindawi

International Journal of Polymer Science

Volume 2018, Article ID 5645797, 9 pages
https://doi.org/10.1155/2018/5645797

Research Article
Effects of Zinc Oxide Nanoparticles on the Properties of
Pectin/Alginate Edible Films

Thi Minh Phuong Ngo,1 Thi Mong Quyen Dang,2 Thi Xo Tran,3
and Pornchai Rachtanapun 4,5
1
The University of Danang - University of Technology and Education, Da Nang, Vietnam
2
College of Food Industry, Da Nang, Vietnam
3
The University of Danang - University of Science and Technology, Da Nang, Vietnam
4
Division of Packaging Technology, Faculty of Agro-Industry, Chiang Mai University, Chiang Mai 50100, Thailand
5
Center of Excellent in Materials Science and Technology, Chiang Mai University, Chiang Mai 50200, Thailand

Correspondence should be addressed to Pornchai Rachtanapun; pornchai.r@cmu.ac.th

Received 9 July 2018; Revised 24 August 2018; Accepted 2 September 2018; Published 22 October 2018

Guest Editor: Ing Kong

Copyright © 2018 Thi Minh Phuong Ngo et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.

This study aimed at developing the functional packaging properties of pectin/alginate films by adding zinc oxide nanoparticles
(ZnO-NPs). The ZnO-NPs were added to the pectin/alginate film at the concentrations of 0.5, 2.5, 5, and 25 g/100 g of blended
polymer. The effects of the ZnO-NP incorporation on the mechanical properties, hydration properties, oxygen permeability,
ultraviolet transmission, transparency, and antimicrobial activity of the films were investigated. The addition of ZnO-NPs from
0 to 5 g/100 g of blended polymer to the pectin/alginate film increased 191.4% of the tensile strength, 169.8% of elongation at
break, and antimicrobial properties (against Aspergillus niger, Colletotrichum gloeosporioides, Escherichia coli, and Saccharomyces
cerevisiae). In contrast, it reduced the solubility from 30.38% to 22.49%, water vapor permeability from 1.01 × 10−14 to
0.414 × 10−14 kg·m/m2·Pa·s, moisture absorption, ultraviolet light transmission, and oxygen permeability from 270.86 × 10−19 to
110.79 × 10−19 kg·m/m2·Pa·s. The effects are the highest when the concentration of the ZnO-NPs in the film was 5 g/100 g of
blended polymer. Attenuated total reflectance-Fourier transform infrared analysis indicated that some interactions between the
ZnO-NPs and pectin/alginate matrices were formed. These results suggest that pectin/alginate/ZnO-NPs films can be used as
active packaging for food preservation.

1. Introduction are largely produced from nontoxic polysaccharide sources.

Food packaging materials with proper mechanical strength;
barrier properties against water, water vapor, and other gases;
thermal stability, recyclability, and biodegradability; and
functional properties, such as antimicrobial activities, are
highly desirable for food safety and extending the shelf-life
of packaged foods [1]. However, biopolymer-based packag-
ing materials have not been widely used in the packaging
industry, mainly because of their poor mechanical, barrier,
and processing properties. They also have a higher produc-
tion cost compared to commodity plastic films [2]. Edible
films are increasingly used in food preservation, and they
Among various polysaccharides, pectin and alginate are par-
ticularly attractive due to their good film-forming property,
moderate mechanical strength, and gas barrier properties
with a unique colloidal nature. Recently, zinc oxide nanopar-
ticles (ZnO-NPs) have become well known for their antimi-
crobial and UV-light barrier properties. The addition of
ZnO-NPs to biopolymers has improved the film’s properties
and showed strong antimicrobial and UV barrier properties
[3]. For these reasons, ZnO-NPs have been applied to food
packaging. However, the antimicrobial activity and mem-
brane properties will depend on the amount of ZnO-NPs
used. Therefore, the main purpose of this study was to
2 International Journal of Polymer Science
SEI 20kV WD10 mmSS30 x25,000 1
휇m
(a)
Figure 1: (a) SEM photographs of ZnO-NPs at magnification of 25,000x and (b) TEM photographs of ZnO-NPs at magnification of 125,000x.
develop pectin/alginate films by mixing ZnO-NPs with dif-
ferent contents and evaluate the effect of them on the proper-
ties of the film.
2. Materials and Methods
2.1. Materials and Sample Preparation. Sodium alginate
(AG), with a molecular weight (M w ) of 1.2 × 106 Da, was pur-
chased from Lianyungang Zhongda Seaweed Industrial Co.
Ltd. (China). Glycerol and calcium chloride were purchased
from Xilong Co. Ltd., China. The BHI medium was pur-
chased from Sigma-Aldrich (St. Louis, USA).
The pectin (P) powder and ZnO-NPs were obtained at
the LAB of the University of Technology and Education,
which belongs to the University of Danang, Vietnam.
The pectin powder was extracted from Yanang leaves
using a heating method with an optimum temperature of
88°C and time of 75minutes and in a 6.5% citric acid solution.
The extracted mixture was precipitated with 96% ethanol.
Then, the mixture was centrifuged (4000 rpm for 10 min)
and washed three times with 96% ethanol. The pectin precip-
itate was dried at 60°C, and the dried pectin was ground into
a flour. The degree of methyl esterification (DE) measure-
ment value was 48.36, and the M w measurement value was
111,105 Da.
The ZnO-NPs were synthesized by the following sol-gel
method: First, 1.1 g of Zn(CH3COO)2·2H2O was dissolved
with 50 ml diethylene glycol. The mixture was stirred con-
tinuously for one hour at 80°C. Then, 50 ml of a 0.1 M
LiOH solution was added to the solution. After stirring
for 5 minutes at 80°C, the white precipitate formed. The
mixture was centrifuged (4000 rpm for 10 minutes) and
washed three times with distilled water and then washed
three times with 96% ethanol to remove the nonreactive
and excess ions. The size of ZnO-NPs was from 20 to
40 nm (Figure 1).
The pectin/alginate film-forming aqueous solutions
were prepared with 2% w/v at the proportion of pectin : al-
ginate 1 : 1 w/w. Powdered calcium chloride was used at
0.01 g/g polymer and glycerol as a plasticizer at 50% (%
w/w of polymer), and both were blended into the pectin-
alginate film-solution. The ZnO-NPs were added in the
QT3_006
100 nm
Print Mag : 12500x @ 51mm
HV = 77.0kV
4 : 15 : 02 a 04/08/16 Direct Mag : 60000x
TEM Mode : Imaging EMLab-NIHE
(b)
pectin/alginate films with glycerol and fabricated with four
levels of ZnO-NPs, namely, 0.5, 2.5, 5, and 25 g/100 g of
blended polymer. The mixture was homogenized using a
homogenizer at speed of 400 rpm in 15 minutes, and after
that, it was stored at 4°C and 90% RH for degassing. To
control the film thickness, the volume of each film-
forming solution poured into a 15 cm × 15 cm mold was
always 60 g. Films were dried at 25°C and at 52 ± 1% rela-
tive humidity (RH) for 24 h by using a fan at speed of
1500 rpm.
The dried films were removed from the mold and
dipped in 5% CaCl2 solution for 20 min to enable cross-
linking [4]. Films were dried at 40°C for two hours in the
oven (UFE 500, Memmert). Films were stored at 52 ± 1%
RH and 25 ± 1°C for 5 days prior to testing.
2.2. Thickness. The thickness of the films was measured
using a Mitutoyo Dial Thickness Gauge (Model PCM 137,
No. 2046S, Japan) with an accuracy of 0.01 mm at 10 random
positions for each film. The average standard deviation was
about 5% of the average thickness. The tests were repeated
three times.
2.3. Tensile Property Measurements and % Elongation at
Break. The tensile properties and % elongation at break of
the samples were measured using an Instron 1141 (Instron
Ltd., Canton, USA) with the procedure according to ASTM
D882-10 [5]. The samples were prepared as sheets using a
gauge length and width of 100 mm and 25 mm, respectively.
The initial grip separation was set at 125 mm/min. The
elongation at break was calculated by dividing the elonga-
tion at the moment of rupture by the initial gauge length
and multiplying by 100. The samples were conditioned at
52 ± 1% RH and 25°C for 48 h prior to testing. There were
ten sample measurements.
2.4. Film Solubility. The films were cut into square
1 cm × 1 cm pieces and dried to a constant weight in a vac-
uum oven at 60°C for 24 hours to obtain the initial film dry
weight (W d ). Each film was then placed in a bottle containing
20 ml distilled water for 24 hours under gentle agitation and
controlled temperature at 25°C. The films were then dried
International Journal of Polymer Science
under the same conditions to obtain the dry weight of water-
leached film (W ws ). The tests were performed in triplicate.
The film solubility was calculated using
W d − W ws
%solubility = × 100 1 Wi
Wd
2.5. Water Contact Angle. Drop shape analysis (DSA30E,
Krüss Co. Ltd., Germany) was used to observe the water
contact angle. The samples were prepared as sheets with
a dimension of 1 cm × 5 cm. Water was dropped onto the
surface of the sheets, and images were taken automatically
every 20 s for 2 min. Samples were kept at 25°C and 52
± 1% RH at least 48 h prior to testing. The measurements
were average from three samples for each formulation [6].
2.6. Water Vapor Permeability (WVP) and Water Vapor
Transmission Rate (WVTR). The WVP of the films was
measured gravimetrically at 25 ± 1°C according to ASTM
E96-00 (ASTM, 2000). Film specimens with an approxi-
mately 8 cm diameter were mounted on the aluminum
cups containing 10 g of silica gel. Paraffin was used to fix
the film specimen on the wide rim of an aluminum cup
[7]. The sealed cups were then weighed and kept in desic-
cators with a saturated solution of Mg(NO3)2 salt that pro-
vided 52 ± 1% RH at 25 ± 1°C throughout the experiment.
The weight gain of the aluminum cups covered with the
films was recorded every 10 hours for 5 days [8]. All tests
were conducted in triplicate. The WVP and WVTR were
calculated using
w·x
WVP = kg · m/Pa · m2 · s , 2 23 ± 2°C, 75% RH, and 760 mmHg following the standard
t · A · Po · RH1 − RH2
w
WVTR = kg/m2 · s , 3
t·A
where w/t is the permeation rate (g/day) that was calcu-
lated by a linear regression of the mass gain versus time
(R2 > 0 99), x is the film average thickness (mm), A is
the permeation area (23.76 cm2), Po is the partial water
vapor pressure at test temperature (3159 kPa at 25°C),
and (RH1 − RH2) is the difference in relative humidity
between the two sides of the film [9].
2.7. Moisture Sorption Isotherm. The films were cut into a
3 cm × 3 cm squares and dried in a hot air oven at 105°C
for 3 h before being placed in desiccators containing dried
silica gel for 2 days. The specimens were then placed in
several different desiccators containing various kinds of
saturated salt solutions to maintain the constant relative
humidity at 11.2%, 33.5%, 53.1%, 64.8%, 75.1%, 85.5%,
and 93.7%. A cotton wool soaked with 96% ethanol was
used as a fungistatic agent in the desiccators containing
the salt solutions with a high relative humidity. The spec-
imens were weighed daily until equilibrium was obtained.
Equilibrium was achieved when the change in weight did
not exceed 0.1% after being weighed for three consecutive
times. The equilibrium moisture content (EMC) (g water/
3
100 g dry solid) of the films at each relative humidity was
calculated using
We
EMC = M i + 1 − 1, 4
where W e is the equilibrium weight of the film specimen
(g), W i is the initial weight of the film specimen (g),
and M i is the initial moisture content of the film specimen
(g water/100 g dry solid) [10, 11]. All measurements were
performed in triplicate.
2.8. Transparency and Light Transmission of Films. Each
film sample was cut into a rectangular piece and directly
mounted between two spectrophotometer magnetic cells.
The transparency and light transmission of the films were
measured at selected wavelengths between 320 and 800 nm
using a UV-Vis spectrophotometer (Model 8451A, Hewlett-
Packard Co., Santa Clara, CA, USA). The film transparency
was calculated with
T 600
Transparency = −log 1/mm , 5
x
where T 600 is the fractional transmittance at 600 nm and x is
the film thickness (mm) [12].
2.9. Oxygen Permeability and Oxygen Transmission Rate. The
oxygen permeability (OP) and oxygen transmission rate
(OTR) were measured using a Mocon Instruments tool
(OX-TRAN® Model 2/21 Series, Mocon Inc., USA). The
measurements were taken using 6 cm × 6 cm film samples at
method [13]. The results are the average over at least three
replicate measurements. The OP was calculated by
OTR · l
OP = kg · m/Pa · m2 · s , 6
ΔP
where OTR is the value of oxygen transmission rate, l is the
thickness of the film, and ΔP is the difference between oxygen
partial pressures between the two sides of the film (Pa).
2.10. Antimicrobial Action of Film-Forming Solutions. The
antimicrobial activities of the film-forming solutions incor-
porating the ZnO-NPs were evaluated by the well diffusion
method in agar against E. coli, Saccharomyces cerevisiae,
Colletotrichum gloeosporioides, and Aspergillus niger. The
microorganisms were prepared for the test as follows: E. coli
was aseptically inoculated in BHI broth and subsequently
incubated at 37°C for 16 h. Saccharomyces cerevisiae, Asper-
gillus niger, and Colletotrichum gloeosporioides were asepti-
cally inoculated in Sabouraud broth and subsequently
incubated at 30°C for 16 h. The evaluation process was as fol-
lows: The Sabouraud agar medium was used for S. cerevisiae,
Aspergillus niger, and Colletotrichum gloeosporioides, and the
BHI agar medium was used for E. coli. All were poured into
petri dishes. After solidification, wells at 5 mm in diameter
were cut from the agar and 0.1 ml of the film-forming
4 International Journal of Polymer Science
Figure 2: Evaluation image of antibacterial action by the “zone
inhibition method.”
solution was carefully poured inside. Next, a 1 ml suspension
containing 106 CFU/ml of each investigated microorganism
was spread in the specific agar medium. After incubating
for 48 h at 30°C for S. cerevisiae, Aspergillus niger, and Col-
letotrichum gloeosporioides and 48 h at 37°C for E. coli, all
plates were inspected. The diameters of the inhibition
zones were measured (in cm) with a ruler on the under-
side of the petri dish. For example, the image that showed
the antibacterial activity of film-forming solution against
E. coli is shown in Figure 2. All measurements were per-
formed in triplicate [14, 15].
2.11. Attenuated Total Reflectance-Fourier Transform
Infrared (ATR-FTIR) Spectroscopy. The reaction between
the pectin, alginate, and ZnO-NPs was monitored by ATR-
FTIR (Thermo Nicolet 6700, USA). The samples were pre-
pared as thin films (about 60 μm). The IR spectra were mea-
sured at wavelengths from 500 cm−1 to 4000 cm−1 and with a
resolution of 4 cm−1.
2.12. Statistical Analysis. Statistics were determined with a
completely randomized design with an analysis of variance
(ANOVA) using Minitab software (version 16.2.3.0; Minitab
Inc., USA). Fisher’s tests were used to compare the difference
among the mean values of the film specimens’ properties at
the level of 0.05. All experiments were conducted in triplicate.
3. Results and Discussion
3.1. Thickness and Mechanical Properties. The thickness and
mechanical properties of the P/AG films with various ZnO-
NP contents are presented in Table 1. The thicknesses of
the P/AG films that contain the ZnO-NPs is higher than for
the P/AG only film. The increase in ZnO-NP content from
0 to 25 g/100 g of blended polymer led to an increase in the
film thickness from 52.4 to 74.6 μm. The increase in the
thickness was not only attributed to the higher solid content
of nanocomposite films ZnO-NPs but also attributed to their
structure. Similar results were reported by Shahmohammadi
Jebel and Almasi [16].
The tensile strength (TS) and % elongation at break (E)
for the films with various ZnO-NP contents equilibrated at
25 ± 1°C and 52 ± 1% RH are shown in Table 1. There was
an increase in tensile strength from 21.71 to 41.56 MPa when
increasing the ZnO-NP content from 0.5 to 5 g/100 g of
blended polymer. On the other hand, the increase in the
ZnO-NP concentration from 5 to 25 g/100 g of blended poly-
mer reduced the tensile strength from 41.56 to 12.79 MPa.
The tensile strength was the highest when the ZnO-NPs were
added at a concentration of 5 g/100 g of blended polymer,
where it reached 191.4% of the tensile strength for the P/
AG film.
The change in elongation is similar to that of tensile
strength. Changes in tensile strength and elongation values
may be due to the formation of hydrogen links between the
pectin, alginate’s hydroxyl groups, and oxygen atoms in the
ZnO-NPs [17, 18]. Moreover, a low concentration of ZnO-
NPs had a negligible effect on the formation of hydrogen
bonds between the OH and the COOH groups in the pec-
tin/alginate matrix, as well as the formation of bonds between
the Ca2+ and the COO− groups of the pectin and alginate
chains. The pectin and alginate chains thereby adopted a
structure that resembles an “egg-box” model.
The decrease in TS and E of the film with 25 g ZnO-NPs/
100 g polymer was probably due to agglomeration of the
ZnO-NPs, the nonuniform distribution of the ZnO-NPs,
and the recrystallization of the ZnO-NPs in the polymer
matrix. These factors caused discontinuous cracks in the
polymer matrix and resulted in a sudden decrease in the TS
and E. A similar result was observed when adding CuO-
NPs and ZnO-NPs into a carrageenan matrix [18].
3.2. Solubility and Water Contact Angle. The water contact
angle (θ) is the most common parameter used to describe
the hydrophilicity of film surfaces. Hydrophilic membranes
possess a contact angle of 0° < θ < 90°, while hydrophobic
membranes have a contact angle of 90° < θ < 180° [19].
Table 2 shows the solubility and water contact angle for the
film specimens.
Results showed that adding ZnO-NPs to the P/AG film at
the amount of 0.5 to 5 g/100 g of blended polymer did not sig-
nificantly change the water contact angle. However, the water
contact angle for the film-incorporated ZnO-NPs with 25 g/
100 g of blended polymer was lower than the other films.
Reducing the water contact angle may be due to an increase
in surface roughness at high ZnO-NP concentrations.
The solubility values for the specimens trended to the
decrease with increasing ZnO-NP content, except for the
ZnO-NP content of 25 g/100 g of blended polymer. These
results indicate that the addition of the ZnO-NPs reduced
the number of hydroxyl groups and charged groups
(−COO−). Moreover, the length of the polymer increased
due to the formation of links between the ZnO-NPs, pectin,
and alginate. Consequently, the solubility of the films was
reduced. The ZnO-NP content in the 25 g/100 g of blended
polymer was more than necessary for creating hydrogen
bonds such that it probably had a negative effect on the
cross-linking between the Ca2+ ion, the pectin, and the algi-
nate carboxyl groups. This increased the solubility value.
International Journal of Polymer Science 5

Table 1: Thickness and mechanical properties (tensile 160

strength = TS; % elongation = %E) of P/AG films with various
140
ZnO-NP contents.
120
ZnO-NP content
(g/100 g of Thickness (μm) TS (MPa) %E (%) 100

EMC, %
blended polymer) 80
0 43.8 ± 2.11d 21.71 ± 1.23d 0.86 ± 0.04c
60
0.5 52.4 ± 2.5c 32.59 ± 1.6c 1.89 ± 0.05b
2.5 56.8 ± 2.83b 36.43 ± 0.98b 1.93 ± 0.05b 40

5 58.1 ± 2.08b 41.56 ± 1.94a 2.32 ± 0.06a 20

25 74.6 ± 3.25a 12.79 ± 0.58e 0.85 ± 0.04c 0
Alphabets in a column indicate a significant difference at P < 0 05 by 0 0.2 0.4 0.6 0.8 1
Duncan’s multiple. Water activity

Table 2: Effect of ZnO-NP contents on the solubility and water P/AG PAG 5.0
contact angle of P/AG films. PAG 0.5 PAG 25
PAG 2.5
ZnO-NP contents
Contact angle (°) Solubility (%)
(g/100 g of blended polymer) Figure 3: Moisture sorption isotherms of P/AG films incorporated
0 73.85 ± 6.4a
30.38 ± 1.3 a with various ZnO-NP contents at 25 ± 1°C.
0.5 72.9 ± 4.5a 27.34 ± 1.8ab
2.5 72.5 ± 2.9a 23.16 ± 2.1b 90
5 70.73 ± 4.1a 22.49 ± 3.1b
25 54.07 ± 7.4b 26.1 ± 1.5ab 80
Light transmission

Alphabets in a column indicate a significant difference at P < 0 05 by

Duncan’s multiple. 70

60
Table 3: WVP and WVTR of P/AG films with various ZnO-NP
contents. 50

ZnO-NP contents (g/100 g of WVP × 10−14 WVRT × 10−7 40

blended polymer) (kg·m/m2·Pa ·s) (kg/m2·s)
0 1.01 ± 0.029a 4.226 ± 0.121a
0.5 0.576 ± 0.018b 2.148 ± 0.069b
2.5 0.447 ± 0.008c 1.949 ± 0.035b
5 0.414 ± 0.02cd 1.486 ± 0.069c
25 0.381 ± 0.019d 1.437 ± 0.069c
Alphabets in a column indicate a significant difference at P < 0 05 by
Duncan’s multiple.
Thus, the film solubility trended to increase when the ZnO-
NP content was 25 g/100 g of blended polymer.
3.3. WVP and WVTR of P/AG Films. Table 3 shows WVP
and WVTR of film specimens. The WVP values of the spec-
imens decreased from 1.01 to 0.414 kg·m/m2·Pa·s (59%), and
WVTR values decreased from 4.226 to 1.486 kg/m2·s
(64.8%), when increasing the ZnO-NP content from 0 to
5 g/100 g of blended polymer. This may be due to the forma-
tion of the hydrogen bonds between the pectin, alginate
matrix, and oxygen atoms in the ZnO-NPs, which increases
the adhesion of the biopolymer matrix and can reduce the
diffusion of the water molecules in the material. A similar
result was reported by Almasi et al. [20]. On the other hand,
the even distribution of the ZnO-NPs with smaller sizes and
300 400 500 600 700 800
Wavelength, nm
P/AG P/AG 25
P/AG 5.0 P/AG 2.5
P/AG 0.5
Figure 4: Light transmission of the films.
filling of the microvoids should reduce the length of a free
path for water uptake. Similar results were reported for the
effect of ZnO-NPs on the WVP of biopolymer-based nano-
composites [3, 21]. There was no significant change in the
WVP and WVTR values of the sample when increasing the
content of the ZnO-NPs from 5 to 25 g/100 g of blended
polymer, which may be due to the maximum reduction
of the hydrophilic groups, such as OH and COOH in
the polymer.
3.4. Moisture Sorption Isotherm. The moisture absorption of
the P/AG film was higher than that of P/AG films with the
ZnO-NPs in the range of water activity between 0.86 and
0.93 (Figure 3). A similar result was reported by Galus and
Lenart [22]. The film’s moisture absorption decreased as
the ZnO-NP content increased. However, there was no
6 International Journal of Polymer Science
Table 4: Transparency of P/AG films with various ZnO-NP contents.
ZnO-NP contents (g/100 g of blended polymer) 0 0.5
Transparency values (1/mm) 3.24 ± 0.02b
Alphabets in a column indicate a significant difference at P < 0 05 by Duncan’s multiple.
Table 5: OP and OTR of P/AG films with various ZnO-NP
contents.
ZnO-NP contents OP × 10−19 OTR × 10−11
(g/100 g of blended polymer) (kg·m/m2·Pa·s) (kg/m2·s)
0 270.86 ± 9.79a 158.65 ± 16.17a
0.5 253.85 ± 15.35a 137.51 ± 6.95b
2.5 191.87 ± 12.44b 89.82 ± 3.68c
5 110.79 ± 7.74d 51.87 ± 3.98d
25 132.92 ± 7.45c 48.84 ± 3.55d
significant change in the moisture absorption between the P/
AG films and the P/AG films with the ZnO-NPs in the water
activity range of 0 to 0.75. Based on the results obtained for
the solubility, WVP, mechanical properties, and moisture
sorption isotherm, it is recognized that these trends are due
to the formation of hydrogen bonding between the OH
groups of the pectin, alginate, and oxygen atoms of the
ZnO-NPs. The reduction in moisture absorption may be
due to the reduction of the free OH groups in the membrane.
On the other hand, a uniform dispersion of smaller ZnO-NPs
and filling of microvoids produces a decrease in the length of
the free path for water uptake.
3.5. Transparency and Light Transmission of Films. Figure 4
shows the light transmission of film specimens. Light trans-
mission decreases in the wavelength range of 320 to 350 nm
(UV light) and reaches the lowest value at 350 nm. The light
transmittance of films containing ZnO-NPs is always lower
than that of films without the ZnO-NPs. The higher the
ZnO concentration in the film, the lower the light transmis-
sion at the wavelength range of 320 to 350 nm. This result
shows that ZnO-NPs in the film have absorbed ultraviolet
light. This result is consistent with that of Khodaiyana et al.
[23] who observed that the UV absorbance of the nanocom-
posite polymers increased as the ZnO-NP content increased.
They also observed that a ZnO-Np content greater than 1%
was necessary to induce UV filtration in a kefiran biopoly-
mer. There is no significant difference in light transmittance
between films containing ZnO-NPs and P/AG films in the
wavelength range of 500 to 800 nm, except for P/AG films
with a ZnO-NP content of 25 g/100 g of blended polymer.
Table 4 shows the transparency of the films with various
ZnO-NP contents. The transparency for the films containing
0.5 to 5 g/100 g blended polymer of ZnO-NPs was not signif-
icantly different from the P/AG film. However, the addition
of ZnO-NPs with 25 g/100 g of blended polymer into the
films decreased the transparency value. The reduction of
transparency of the films with a concentration of 25 g ZnO-
NPs/100 g polymer may be due to the over-distribution of
the ZnO-NPs in the pectin/alginate network.
2.5 5 25
3.26 ± 0.01b 3.25 ± 0.03b 3.17 ± 0.02ab 3.01 ± 0.02a
3.6. Oxygen Permeability and Oxygen Transmission Rate. The
OP and OTR of P/AG and P/AG films with various ZnO-NP
contents are presented in Table 5.
The addition of ZnO-NP to the P/AG films led to a
reduced oxygen permeability. The lowest reduction occurred
when the ZnO-NP concentration reached 5 g/100 g of poly-
mer. The OP values decreased by 59%, and OTR values
decreased by 67.3% with the addition of 5 g ZnO-NPs/100 g
of blended polymer. The permeability coefficient of a sub-
stance is determined by the formula P = D × S, in which D
is the diffusion coefficient and S is the solubility coefficient
[24]. The reduction of OP and OTR can be attributed to
the distribution of the ZnO nanoparticles in the film matrix,
which led to a reduced oxygen diffusion. The increase in OP
when the concentration of ZnO-NPs was 25 g/100 g of
blended polymer was probably due to reducing the hydrogen
bonds in the pectin/alginate matrix and reducing the interac-
tion between P/AG and ZnO-NPs, due to structural changes
in the polymer matrix. Therefore, the diffusion coefficient
increased leading to an increase in the oxygen permeability
of these films. This result shows the possibility of using
P/AG membranes with ZnO-NPs in food preservation to
inhibit oxidation.
3.7. Antimicrobial Action of Film-Forming Solutions. The
antimicrobial activities of the P/AG ZnO-NPs films against
Escherichia coli, Saccharomyces cerevisiae, Colletotrichum
gloeosporioides, and Aspergillus niger are shown in Figure 5.
The inhibition zone increased with the increase of the
ZnO-NP concentration in the range of 0.5 to 5 g/100 g of
polymer. However, when increasing the concentration from
5 g to 25 g/100 g of polymer, the inhibitory zone did not
increase. This may be related to the decrease of the diffusion
ability of the ZnO-NPs in the agar at high concentrations.
The antimicrobial effect was due to the ZnO-NPs because
the pure P/AG film that did not contain ZnO-NPs was
not antibacterial. The inhibitory effect of the ZnO-NPs
against Aspergillus niger and Colletotrichum gloeosporioides
was greater than that against E. coli and Saccharomyces cer-
evisiae. It is believed that the antimicrobial activity of ZnO-
NPs is mainly dependent on the cell wall structure of the
microorganisms. In almost mold, the hyphal cell wall con-
sists of a single, 80 to 150 nm layer composed of chitin
and β-glucan. In contrast, the 200 to 600 nm thick yeast cell
wall has three layers [25]. The cell wall of E. coli (Gram-
negative bacteria) is composed of a complex structure with
thin peptidoglycan layer surrounded by an outer membrane
[26, 27]. The antimicrobial activity of the P/AG films with
ZnO-NPs was the highest when the ZnO-NP concentration
was 5 g/100 g of blended polymer. The results of the study
on the antimicrobial properties of P/AG films with ZnO-
NPs support the use of this material to preserve food prod-
ucts, especially products that are susceptible to mold damage.
International Journal of Polymer Science 7

3.0

2.5

Antimicrobial diameter,cm
2.0

1.5

1.0

0.5

0.0
0 0.5 2.5 5 25
ZnO-NP contents

E.Coli A.niger
S.cerevisiae Colletotrichum. gls

Figure 5: Antimicrobial activities of P/AG films with various ZnO-NP contents.

120
P/AG/25%ZnO-NPs

100 P/AG/5%ZnO-NPs

80
% transmittance

60

40
P/AG/2.5%ZnO-NPs
20 P/AG/0.5%ZnO-NPs
P/AG
0
4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers (cm‒)

Figure 6: FTIR spectra of P/AG films incorporated with various ZnO-NP contents.

Moreover, ZnO-NPs have a negligible negative effect on
human cells according to Reddy et al. [28].
3.8. FTIR Spectra of P/AG Films with ZnO-NPs. The
ATR-FTIR analysis demonstrates the interaction between
the ZnO-NPs, pectin, and alginate. The results are shown
in Figure 6.
The results show that the spectra for all films have char-
acteristic peaks at 4000–500 cm−1. The P/AG films exhibited
the major band at 1630 cm−1, which is the characteristic peak
of C=O stretching/hydrogen bonding coupled with a COO−
group of pectin and alginate [25]. The absorption peaks at
1400 and 1440 cm−1 are related to the stretching bands of
the COO− groups, and the peak at 3410 cm−1 was induced
by the OH groups. The ATR-FTIR spectra of P/AG/ZnO-
NPs films show that the peaks at 3410, 2890, 1630, and
1420 cm−1 were shifted to 3300–3200, 2920–2910, 1597,
and 1410 cm−1, respectively. Shifting of the adsorption peaks
indicates that hydrogen bonds between the oxygen atoms of
ZnO-NPs and the OH, the COOH, and the CH3 (hexane)
groups of pectin/alginate matrix occurred. These results con-
firm that the addition of ZnO-NPs can improve the water
resistance, oxygen resistance, and mechanical properties of
the P/AG films. The reason could be that the OH and the
COOH groups of the pectin/alginate matrix are able to form
hydrogen bonds with oxygen groups in the ZnO-NPs.
4. Conclusions
The addition of ZnO-NPs to pectin and alginate films chan-
ged some physicochemical properties of films compared to
films without the ZnO-NPs. There was a decrease in the sol-
ubility, moisture absorption, UV light transmission, WVP,
WVTR, OP, and the OTR of the P/AG films with ZnO-NPs
compared to the films without them. In contrast, there was
an increase in tensile strength, elongation at break, and
8 International Journal of Polymer Science
antimicrobial properties of the P/AG films with ZnO-NPs
compared to the films without them. In this work, the change
was the highest when the ZnO-NP content in the film was
5 g/100 g of blended polymer. The ATR-FTIR analysis indi-
cated that hydrogen bonds between the ZnO-NPs and pec-
tin/alginate matrices were formed. These results suggest the
possibility of using P/AG/ZnO-NPs film in food preservation
and that they may be better than pectin/alginate films.
Data Availability
The data used to support the findings of this study are
available from the corresponding author upon request.
Conflicts of Interest
The authors declare that they have no conflicts of interest.
Acknowledgments
The authors gratefully acknowledge the financial support
from the “911 Scholarship” for Ph.D. students from the Min-
istry of Education, Vietnam. We would also like to thank the
Faculty of Chemical Engineering, University of Technology
& Education (UTE) and University of Technology & Science
(DUT), the University of Danang for the equipment and
facility support. We wish to thank the Center of Excellence
in Materials Science and Technology, Chiang Mai University,
for the financial support under the administration of Mate-
rials Science Research Center, Faculty of Science, Chiang
Mai University.
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